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Issue 4, 2013
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Tuning of gallery heights in a crystalline 2D carbon nitride network

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Abstract

Poly(triazine imide)—a 2D layered network—can be obtained as an intercalation compound with halides from the ionothermal condensation of dicyandiamide in a eutectic salt melt. The gallery height of the intercalated material can be tuned via the composition of the eutectic melt and by post-synthetic modification. Here, we report the synthesis of poly(triazine imide) with intercalated bromide ions (PTI/Br) from a lithium bromide and potassium bromide salt melt. PTI/Br has a hexagonal unit-cell (P63cm (no. 185); a = 8.500390(68) Å, c = 7.04483(17) Å) that contains two layers of imide-bridged triazine (C3N3) units stacked in an AB-fashion as corroborated by solid-state NMR, FTIR spectroscopy and high-resolution TEM. By comparison with a recently reported material PTI/Li+Cl, prepared from a LiCl/KCl eutectic, the layer-stacking distance in the analogous bromide material was expanded from 3.38 Å to 3.52 Å – an exceptionally large spacing for an aromatic, discotic system (cf. graphite 3.35 Å). Subsequent treatment of PTI/Br with concentrated ammonium fluoride yields poly(triazine imide) with intercalated fluoride ions (PTI/F) (P63/m (no. 176); a = 8.4212(4) Å, c = 6.6381(5) Å) as a statistical phase mix with PTI/Br. Fluoride intercalation leads to a contraction of the gallery height to 3.32 Å, demonstrating that the gallery height is synthetically tuneable in these materials.

Graphical abstract: Tuning of gallery heights in a crystalline 2D carbon nitride network

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Article information


Submitted
12 Nov 2012
Accepted
12 Nov 2012
First published
12 Nov 2012

J. Mater. Chem. A, 2013,1, 1102-1107
Article type
Paper

Tuning of gallery heights in a crystalline 2D carbon nitride network

S. Y. Chong, J. T. A. Jones, Y. Z. Khimyak, A. I. Cooper, A. Thomas, M. Antonietti and M. J. Bojdys, J. Mater. Chem. A, 2013, 1, 1102
DOI: 10.1039/C2TA01068B

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